WO2024013341A1 - Produit oligomère obtenu a partir d'huile de pyrolyse par polymérisation - Google Patents

Produit oligomère obtenu a partir d'huile de pyrolyse par polymérisation Download PDF

Info

Publication number
WO2024013341A1
WO2024013341A1 PCT/EP2023/069561 EP2023069561W WO2024013341A1 WO 2024013341 A1 WO2024013341 A1 WO 2024013341A1 EP 2023069561 W EP2023069561 W EP 2023069561W WO 2024013341 A1 WO2024013341 A1 WO 2024013341A1
Authority
WO
WIPO (PCT)
Prior art keywords
stream
ranging
oligomeric product
feedstream
pyrolysis
Prior art date
Application number
PCT/EP2023/069561
Other languages
English (en)
Inventor
Benjamin BIBER
Christine Richardson
Keith Nelson
Original Assignee
Totalenergies Onetech
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Totalenergies Onetech filed Critical Totalenergies Onetech
Publication of WO2024013341A1 publication Critical patent/WO2024013341A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/50—Partial depolymerisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/09—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by filtration
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the disclosure relates to the preparation of an oligomeric product prepared from a pyrolysis oil.
  • the disclosure relates to the polymerization via polymerization on the oil obtained preferably from the pyrolysis of plastic in order to obtain an oligomeric product that can be further used in rubber applications, additive compositions, or other commercial applications.
  • Waste streams and particular waste plastics are mostly diverted to landfills or incinerated, with a smaller fraction diverting to recycling. There is however a strong need, influenced by the regulations to limit waste plastic in landfills. On the other hand, waste plastics disposal into landfills is becoming increasingly difficult. There is therefore a need for recycling waste plastics.
  • plastic pyrolysis A possible route to recycle plastic is via plastic pyrolysis.
  • the pyrolysis plastic oil obtained from plastic pyrolysis generally is generally not easily valorised.
  • the pyrolysis plastic oil contains large quantities of impurities and also large quantities of dienes and of olefins.
  • US2012/149953 discloses oligomerizing one or more olefins having a boiling point less than 82°C. in a presence of an ionic liquid catalyst and one or more C5+ alpha olefins in a reactor to produce a base oil having a kinematic viscosity at 100° C. of 36 mm2/s or higher and a VI greater than 55; and wherein the one or more olefins having the boiling point less than 82° C. comprise greater than 50 wt % of a total mixture of olefins fed to the reactor.
  • F. Sadaka et al. (Polymer Degradation and Stability 98 (2013) 736e742) describe the metathetic degradation of synthetic cis-1 ,4-polyisoprene (PI) and styrene-butadiene copolymer (SBR) that was performed with cis-1 ,4-diacetoxy-2-butene (DAB) as chain transfer agent (CTA) using Grubbs II catalyst.
  • Well-defined acetoxy telechelic polyisoprene structures were obtained in a selective manner with a wide range of targeted average molecular weights from 350 g moll to 98,000 g.mol' 1 , with a polydispersity index of around 2.
  • the aim of the present disclosure is to provide a valorization route for the polymerizable materials in pyrolysis oil. More precisely, the aim of the present disclosure is to convert the dienes present in the pyrolysis oil, being preferably a plastic pyrolysis oil, into valuable oligomeric products.
  • the polymerization is 2-fold: it serves to remove contaminants that foul catalysts further downstream in the refining process of the pyrolysis oil and to convert those contaminants into a useable material, i.e., liquid resin.
  • the disclosure provides an oligomeric product remarkable in that it is prepared via polymerization from a liquified waste polymer and in that the oligomeric product has a number average molecular weight (Mn) ranging from 100 to 950 g/mol measured using gel permeation chromatography and an aromatic content ranging from 0.1 wt.% to less than 50 wt.% as determined by 1 H NMR.
  • Mn number average molecular weight
  • the oligomeric product shows an olefinic content of at most 20.0 wt. % as determined by 1 H NMR.
  • the oligomeric product an olefinic content ranging from 0.1 to 20.0 wt.%; preferably from 0.3 to 15.0 wt.%; more preferably, from 0.5 to 10.0 wt.%. from 0.8 to 5.0 wt.%.
  • the oligomeric product shows an aliphatic content ranging from 15 to 100 wt.% as determined by 1 H NMR; preferably ranging from 40.0 to 99.5 wt.%; more preferably ranging from 50.0 to 99.0 wt.%; even more preferably ranging from 70.0 to 98.5 wt.%; and most preferably ranging from 80.0 to 98.0 wt.%.
  • the oligomeric product shows an aromatic content ranging from 0.3 to 45.0 wt.% as determined by 1 H NMR; preferably ranging from 0.5 to 40.0 wt.%; more preferably ranging from 0.8 to 30.0 wt.%; and even more preferably ranging from 1 .0 to 20.0 wt.%.
  • the oligomeric product has viscosity at 30°C ranging from 10 to 50 000 cps measured using a Brookfield viscometer; preferably ranging from 10 to 50 000 cps; more ranging from 10 to 10 000 cps; even more preferably ranging from 10 to 4 000 cps; and most preferably ranging from 10 to 2 500 cps.
  • the oligomeric product has a number average molecular weight (Mn) ranging from 120 to 700 g/mol measured using gel permeation chromatography and a polystyrene calibration; preferably from 150 to 650 g/mol; and more preferably from 200 to 550 g/mol.
  • Mn number average molecular weight
  • the oligomeric product has a weight average molecular weight (Mw) ranging from 100 to 10,000 g/mol measured using gel permeation chromatography and a polystyrene calibration; preferably from 120 to 5,000 g/mol; more preferably from 150 to 3,500 g/mol; and even more preferably from 200 to 2,000 g/mol.
  • Mw weight average molecular weight
  • the oligomeric product has a z-average molecular weight (Mz) ranging from 100 to 100,000 g/mol measured using gel permeation chromatography and a polystyrene calibration; preferably from 120 to 85,000 g/mol; more preferably from 150 to 70,000 g/mol; and even more preferably from 200 to 50,000 g/mol.
  • Mz z-average molecular weight
  • the oligomeric product has a Mw/Mn ranging from 1.0 to 10.0; preferably from 1 .0 to 5.0; more preferably from 1 .0 to 4.0; and even more preferably from 1 .1 to 2.8.
  • the oligomeric product comprises a comonomer selected from the group consisting of styrene, alpha-methyl styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 4-t-butyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2,4-diisopropyl styrene, 2.4.6- trimethyl styrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl) styrene, 1 -vinyl naphthalene, 2-vinyl naphthalene, vinyl anthracene, 4-methoxy styrene, monochlorostyrene, dichlorostyrene, divinyl benzene, Indene, methyl-lndene, and mixtures thereof
  • the oligomeric product comprises a comonomer wherein the comonomer is present at a concentration ranging from 0.01 to 90 mol.% based on the total weight of the oligomeric product, preferably from 1.0 to 80 mol.%.
  • the oligomeric product is a wax and/or it shows a crystallisation temperature (Tc) below 35°C; preferably ranging from 18 to 32°C; more preferably ranging from 20 to 30°C; and even more preferably ranging from 21 to 29°C.
  • the oligomeric product is a resin and/or it shows a glass transition temperature (Tg) below -20°C as determined by Differential Scanning calorimetry; preferably ranging from - 60°C to - 25°C; more preferably from -50°C to -30°C; and even more preferably from -49°C to - 35°C.
  • the disclosure relates to a rubber composition
  • a rubber composition comprising: a) At least one elastomer selected from synthetic and natural elastomers; b) A curing agent; and c) An oligomeric product prepared from a liquified waste polymer according to the first aspect.
  • the content of said at least one elastomer in the rubber composition ranges from 1 to 150 phr; preferably, from 1 to 120 phr; more preferably from 1 to 100 phr; from 50 to 150 phr.
  • the content of said curative agent in the rubber composition ranges from 0.1 - 25 phr; preferably, from 0.5 to 22 phr; more preferably from 1 to 20 phr, even more preferably from 5 to 18 phr.
  • the content of said oligomeric product in the rubber composition ranges from 0.1 to 50 phr; preferably, from 0.5 to 40 phr; more preferably from 1 to 30 phr, even more preferably from 5 to 25 phr.
  • the oligomeric product used in the rubber composition is having a number average molecular weight, Mn, ranging from 100 to 10 000 g/mol measured using gel permeation chromatography and a polystyrene calibration and wherein the oligomeric product shows a glass transition temperature (Tg) below -20°C as determined by Differential Scanning calorimetry or a crystallisation temperature below 35°C.
  • Mn number average molecular weight
  • the disclosure related to an adhesive composition comprising a tackifying resin comprising said oligomeric product according to the first aspect.
  • the disclosure related to process for preparing an oligomeric product follows the following steps: a) providing a feedstream containing liquified waste polymer, wherein said feedstream contains at least 0.1 wt. % to at most 50 wt.
  • the process further comprises a step h) preparing a rubber composition comprising at least one elastomer selected from synthetic and natural elastomers; a curing agent; and said oligomeric recovered at step g).
  • the liquified waste polymer is a pyrolysis plastic oil
  • step a) of providing a feedstream containing liquified waste polymer comprises the preliminary steps of preparation of liquified waste polymer including: a1) of providing a waste plastics stream; a2) pyrolyzing said waste plastics stream at a temperature of at least 200°C; a3) recovering a pyrolizer effluent and separating, into a C1 to C4 hydrocarbons fraction, a fraction having a boiling range higher than 350°C and a remaining fraction being said pyrolysis plastic oil; a4) optionally sending the fraction having a boiling range higher than 350°C into a Fluid Catalytic Cracking (FCC) unit, or a hydrocracking unit, a coker or a visbreaker or blending said fraction having a boiling range higher than 350°C in crude oil or in a crude oil cut to be further refined.
  • FCC Fluid Catalytic Cracking
  • the process further comprises a step b) of drying the feedstream to obtain a dried feedstream wherein step b) is performed before step c) of polymerization so that step c) of polymerization reaction is performed on the dried feedstream.
  • the process in step b) for drying is performed and comprises a sub-step b1 ) of decantation and/or centrifugation. More preferably, the first sub-step b1) is followed by a second sub-step b2) of drying using a molecular sieve to reach a water content of less than 0.1 vol.% according to ASTM D95-13 (2016).
  • the feedstream contains at least 75 wt.% of the liquefied waste polymer based on the total weight of the feed stream.
  • Step c) comprises performing a polymerization reaction preferably a cationic polymerization or a free radical polymerization or an anionic polymerization.
  • the polymerization reaction is a cationic polymerization. More preferably, the polymerization reaction in step c) is a cationic polymerization performed in the presence of an acidic catalyst; with preference, the acidic catalyst is a Brdnsted acid or a Lewis acid.
  • the polymerization reaction in step c) is a cationic polymerization performed in the presence of an acidic catalyst being a Lewis acid chosen among BF 3 , complexes of boron trifluoride, AICI 3 , SnCI 4 , ZnCI 2 , FeCI 3 and TiCI 3 , alkyl aluminum chlorides, H 2 SO 4 or any mixture thereof; with preference, the acidic catalyst is or comprises boron trifluoride etherate.
  • an acidic catalyst being a Lewis acid chosen among BF 3 , complexes of boron trifluoride, AICI 3 , SnCI 4 , ZnCI 2 , FeCI 3 and TiCI 3 , alkyl aluminum chlorides, H 2 SO 4 or any mixture thereof; with preference, the acidic catalyst is or comprises boron trifluoride etherate.
  • the acid catalyst process is present at a concentration ranging from 0.5 wt. % to 5.0 wt. % based on the total weight of said feedstream; and/or in that the polymerization reaction of step c) is carried out until the dienes of the purified liquified waste polymer are less than 5.0 wt. % based on the total weight of the first product stream.
  • the polymerization conditions of step (c) comprise a contact time ranging from 5 min to 5 hours; and/or a temperature ranging from 5 to 100°C at atmospheric pressure.
  • the polymerization reaction of step c) is performed in the presence of one or more comonomers; with preference, the one or more comonomers comprise a vinyl aromatic and/or the one or more comonomers are present at a concentration from 1 .0 to 25.0 wt. % based on the total weight of the liquified waste polymer.
  • the basic compound forms a basic stream; wherein the basic stream and the first product stream are contacted with a weight ratio ranging from 1 :1 to 1 :1 ,000.
  • step: d) is performed and the concentration of the basic compound ranges from 0.1 to 50.0 wt.% based on the total weight of said neutralized product stream.
  • step d) is performed and the basic compound: has a pKa in water ranging from 7.5 to 14; and/or
  • step d) is performed in continuous mode; and/or the removal of said basic compound from neutralized product stream, to obtain a second product stream, is performed by decantation and/or by centrifugation.
  • the process further comprises a step e) of washing the first product stream, or the second product stream with a solvent to obtain a washed stream; with preference, the washing is performed at a temperature ranging from 5°C to 95 °C.
  • the solvent is selected from water or an aqueous acidic solution comprising one or more organic acids selected from citric acid (C 6 H 8 O 7 ), formic acid (CH 2 O 2 ), acetic acid (CH 3 COOH), sulfamic acid (H 3 NSO 3 ) and any combination thereof and/or one or more inorganic acids selected from hydrochloric acid (HCI), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 ), and any combination thereof.
  • organic acids selected from citric acid (C 6 H 8 O 7 ), formic acid (CH 2 O 2 ), acetic acid (CH 3 COOH), sulfamic acid (H 3 NSO 3 ) and any combination thereof and/or one or more inorganic acids selected from hydrochloric acid (HCI), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 ), and any combination thereof.
  • the washing step is carried out until the pH of said washed stream reached is in the range of 5.0 to 9.0; and/or the washing is followed by a decantation and/or a centrifugation to separate the solvent from washed stream.
  • the process further comprises a step f) of filtering the stream obtained in the previous step to obtain a filtered stream wherein the filtering is performed to remove solids from the first product stream orfrom the second product stream orfrom the washed stream, and/or to coalesce remaining traces of solvent if any; with preference, the filtering step is followed by a dewatering step.
  • the step g) of separation is performed via distillation or steam distillation or vacuum stripping or fractional distillation, or any combination.
  • purified and liquefied waste polymer is recovered and blended in the fuel pool; with preference, the purified liquified waste polymer is separated in a naphtha cut having a boiling range of less than 150°C and a diesel cut having a boiling range between 150 and 350°C wherein said naphtha cut is incorporated in a naphtha pool, said diesel cut is incorporated in a diesel pool.
  • the liquified waste polymer in the feedstream has a final boiling point of at most 700°C; and/or the feedstream contains from 0.1 to 25.0 wt.% of dienes based on the total weight of said feedstream.
  • the oligomeric product is recovered and mixed with an elastomer, a curing agent, and a filler to obtain a rubber composition or is used as a tackifying resin and mixed with an elastomer to form an adhesive composition.
  • the disclosure provides an installation for carrying out the process of the fourth aspect, said installation is remarkable in that it comprises: a polymerization section; an optional neutralization section; a separation section; wherein the polymerization section and the separation section are fluidically connected in series, and wherein the neutralization section when present is placed downstream of the polymerization section and upstream of the separation section.
  • the installation comprises: a pre-treatment section comprising a pyrolysis unit, one or more separation units, and an optional washing unit; a drying section comprising a decanter and/or a centrifuge; and/or a molecular sieve; a polymerization section comprising one or more polymerization reactors; preferably loaded with an acidic catalyst; a neutralization section a mixing reactor and an optional separation unit comprising at least one selected from a decanter, a centrifuge, and a filter; a washing section comprising a mixing vessel and a separation unit comprising a decanter and/or a centrifuge; a filtering section comprising a filter and an optional molecular sieve.
  • a separation section comprising a separation unit comprising one or more distillation columns.
  • the disclosure provides a method to produce an adhesive composition
  • a method to produce an adhesive composition comprising the production of an oligomeric product according to the process of the fourth aspect; and mixing the recovered oligomeric product with an elastomer to form an adhesive composition; wherein the oligomeric product is a liquid resin prepared from a liquified waste polymer and used as a tackifying resin.
  • the liquified waste polymer is firstly optionally dried, sent to the cationic polymerization to convert the dienes into oligomeric products.
  • the effluents of the cationic polymerization are then sent to an optional treatment with a basic compound followed by the removal of the basic compound and followed by an optional washing step.
  • the various fractions are separated into various fractions depending on the boiling point. If a heavy fraction can be separated, it is sent to conversion units.
  • the oligomeric product that is converted into resins can also be separated. If a remaining fraction of purified plastic oil fraction is present it can be sent to a hydrotreatment or a cracking or a steam cracking to produce olefins being further polymerized.
  • the oligomeric product obtained can also be used as valuable resins.
  • Figure 2 presents the calibration curve for maleic anhydride concentration.
  • Figure 3 presents the 1 H NMR olefinic content of treated pyrolysis oil compared to crude pyrolysis oil of examples 2 to 4.
  • Figure 4 presents the olefinic carbon stretching peak areas from FTIR of examples 2 to 4.
  • Figure 5 presents the viscosity of Adhesive Formulations at 160°C relating to example 6
  • Figure 6 presents the 180° Peel Adhesion Testing on SS relating to example 6.
  • Figure 7 presents the 180° Peel Adhesion Testing on HDPE relating to example 6
  • Figure 8 presents the 180° Peel Adhesion Testing on CC relating to example 6.
  • Figure 9 presents the Loop Tack Results on SS relating to example 6.
  • Figure 10 presents the Loop Tack Results on HDPE relating to example 6
  • Figure 11 presents the Loop Tack Results on CC relating to example 6
  • Figure 12 presents the Quick Stick Results on SS relating to example 6
  • Figure 13 presents the Quick Stick Results on HDPE relating to example 6
  • Figure 14 presents the Quick Stick Results on CC relating to example 6
  • Figure 15 presents the Room Temperature Shear Results on SS relating to example 6
  • Figure 16 presents the room Temperature Shear Results on Kraft Paper relating to example 6.
  • Figure 17 presents the SAFT Results on SS relating to example 6
  • Figure 18 presents the SAFT Results on Kraft Paper relating to example 6
  • Figure 19 is an example of installation according to the disclosure.
  • alkane or “alkanes” as used herein describe acyclic branched or unbranched hydrocarbons having the general formula CnH2n+2, and therefore consisting entirely of hydrogen atoms and saturated carbon atoms; see e.g., IUPAC. Compendium of Chemical Terminology, 2nd ed. (1997).
  • alkanes accordingly describes unbranched alkanes ("normal-paraffins” or “n-paraffins” or “n-alkanes” or “paraffins”) and branched alkanes (“iso-paraffins” or “isoalkanes”) but excludes naphthenes (cycloalkanes). They are sometimes referred to by the symbol
  • hydrocarbon refers to the alkanes (saturated hydrocarbons), cycloalkanes, aromatics and unsaturated hydrocarbons together.
  • conversion means the mole fraction (i.e. , percent) of a reactant converted to a product or products.
  • selectivity refers to the percentage of converted reactant that went to a specified product.
  • vol.% or “mol.%” refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt. % of components.
  • naphtha refers to the general definition used in the oil and gas industry. In particular, it refers a hydrocarbon originating from crude oil distillation having a boiling range from 15 to 250°C as measured by ASTM D2887-22e1. Naphtha contains substantially no olefins as the hydrocarbons originates from crude oil. It is generally considered that a naphtha has carbon number between C3 and C11 , although the carbon number can reach in some case C15. It is also generally admitted that the density of naphtha ranges from 0.65 to 0.77 g/mL.
  • oil refers to the general definition used in the oil and gas industry. In particular, it refers a hydrocarbon having a boiling point in the range of 250 to 350°C as measured according to the ASTM D7500-15(2019).
  • waste polymer refers to any hydrocarbon liquid obtained from a waste polymer, preferably obtained from a waste plastic.
  • process such as hydrothermal liquefaction or thermal pyrolysis or catalytic pyrolysis or steam pyrolysis or even pyrolysis in the presence of hydrogen of waste polymer can be used.
  • the waste polymers encompass any polymer that are considered as waste such as waste polyethylene (PE), waste polypropylene (PP), waste polyethylene terephthalate (PET), waste poly vinyl chlorine (PVC) but also other polymers originating from waste or used tires for instance.
  • waste polyethylene PE
  • PP waste polypropylene
  • PET waste polyethylene terephthalate
  • PVC waste poly vinyl chlorine
  • the term “liquified waste polymer” also encompasses “pyrolysis plastic oil”.
  • pyrolysis plastic oil refers to the liquid products obtained once waste plastic have been thermally pyrolyzed.
  • the pyrolysis process shall be understood as an unselective thermal cracking process.
  • the pyrolysis involves the breaking of the polymer chains by heating. Rather than breaking the polymer down to its original monomers, pyrolysis tends to make a range of shorter chain compounds, similar in many ways to the mixtures of hydrocarbons found in crude oil and oil products. A catalyst is sometimes used to reduce the operating temperature.
  • the plastic being pyrolyzed can be of any type.
  • the plastic being pyrolyzed can be polyethylene, polypropylene, polystyrene, polyesters, polyamides, polycarbonates etc.
  • liquified waste polymers contain paraffins, i-paraffins (iso-paraffins), dienes, alkynes, olefins, naphthenes, and aromatic components. Liquified waste polymer may also contain impurities such as organic chlorides, organic silicon compounds, metals, salts, oxygenates, sulfur and nitrogen compounds, etc.
  • the origin of the plastic is the waste plastic without limitation on the origin or on the nature of the plastic.
  • the composition of the liquified waste polymer is dependent on the type of plastic pyrolyzed. It is however mainly constituted of hydrocarbons having from 1 to 50 carbon atoms and impurities.
  • paraffin The content in paraffin, naphthene, olefin, and aromatic is determined according to the standardized method UOP990-11.
  • This method uses two-dimensional gas chromatography (GCxGC) coupled with a flame ionization detector (FID).
  • GCxGC two-dimensional gas chromatography
  • FID flame ionization detector
  • Diene Value (DV) or Maleic Anhydride Value (MAV) corresponds to the amount of maleic anhydride (expressed as equivalents of iodine) which will react with 100 parts of oil under specific conditions. It is a measure of the conjugated double bonds in the oil. One mole of Maleic anhydride corresponds to 1 conjugated double bond.
  • Diene Value (DV) refers to the analytical method by titration expressed in g of iodine per 100 g of sample.
  • MAV Maleic Anhydride value
  • bromine number corresponds to the amount of bromine in grams reacted by 100 grams of a sample. The number indicates the quantity of olefins in a sample. It is determined in grams of Br2 per 100 grams of solution (gBr2/100g) and can be measured for instance according to the method ASTM D1159-07(2017).
  • bromine index is the number of milligrams of bromine that react with 100 grams of sample. It is determined in milligrams of Br2 per 100 g of solution (mg Br2/100g) and can be measured for instance according to the method ASTM D2710-20.
  • boiling point used refers to the boiling point generally used in the oil and gas industry. They are measured at atmospheric pressure.
  • the initial boiling point is defined as the temperature value when the first bubble of vapor is formed.
  • the final boiling point is the highest temperature that can be reached during a standard distillation. At this temperature, no more vapor can be driven over into the condensing units.
  • the determination of the initial and the final boiling point is known per se in the art.
  • the boiling range of the mixture they can be determined using various standardized methods such as for instance the ASTM D2887-22e1 relating to the boiling range distribution of petroleum fractions by gas chromatography. For compositions containing heavier hydrocarbons the ASTM D7169-20e1 can alternatively be used.
  • the boiling ranges of the distillates can also advantageously be measured using the ASTM D7500-15(2019) or the standard NF EN 15199-1. Due to the nature of the liquified waste polymer, the preferred method for the measurement of the boiling point is the method NF EN 15199-1. Depending on the method, up to 10°C of difference can be evidenced. Hence, the boiling point expressed here is to be considered with an absolute uncertainty of +/- 10°C.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mz z average molecular weight
  • d molecular weight distribution
  • Agilent 1260 Series Degasser Part Number G1322A
  • Agilent 1260 Series Isocratic Pump Part Number G1310B
  • Agilent 1260 Series Autosampler Part Number G1329B
  • Agilent 1260 Series Thermostatted Column Compartment Part Number G1316A
  • Agilent 1260 Series Multiple Wavelength Detector Part Number G1365C
  • Agilent 1260 Series Refractive Index Detector Part Number G1362A.
  • Sample Preparation Weighed approximately 0.06 grams of sample into a vial. Dissolve in 10 ml THF then filter through a 0.45 micron PTFE membrane. Run sample the same day it is prepared.
  • M n number average
  • M w weight average
  • M z z average
  • Ni and W are the number and weight, respectively, of molecules having molecular weight Mi.
  • the molecular weight distribution (MWD) is then calculated as Mw/Mn.
  • the crystallization temperature (Tc) and the glass temperature transition (Tg) were measured using differential scanning calorimetry (DSC), TA Instruments Q2000 equipped with a Liquid Nitrogen Cooling System (LNCS).
  • the software was TA Instruments Universal Analysis 2000 Version 4.5A. We used a temperature ramp with a ramp rate of 10°C/min.
  • the liquid resin comprises a low molecular weight pyrolysis oil-based homopolymer or copolymer resin obtained using a Friedel-Crafts catalyst and preferably has a low viscosity and some aromatic content.
  • the disclosure provides an oligomeric product remarkable in that it is prepared via polymerization from a liquified waste polymer and in that the oligomeric product has a number average molecular weight (Mn) ranging from 100 to 950 g/mol measured using gel permeation chromatography and an aromatic content ranging from 0.1 wt.% to less than 50 wt.% as determined by 1 H NMR.
  • Mn number average molecular weight
  • the oligomeric product shows an olefinic content of at most 20.0 wt. % as determined by 1 H NMR.
  • the oligomeric product has an olefinic content ranging from 0.1 to 20.0 wt.%; preferably from 0.3 to 15.0 wt.%; more preferably, from 0.5 to 10.0 wt.%. from 0.8 to 5.0 wt.%.
  • the oligomeric product shows an aliphatic content ranging from 15 to 100 wt.% as determined by 1 H NMR; preferably ranging from 40.0 to 99.5 wt.%; more preferably ranging from 50.0 to 99.0 wt.%; even more preferably ranging from 70.0 to 98.5 wt.%; and most preferably ranging from 80.0 to 98.0 wt.%.
  • the oligomeric product shows an aromatic content ranging from 0.3 to 45.0 wt.% as determined by 1 H NMR; preferably ranging from 0.5 to 40.0 wt.%; more preferably ranging from 0.8 to 30.0 wt.%; and even more preferably ranging from 1 .0 to 20.0 wt.%.
  • the oligomeric product has viscosity at 30°C ranging from 10 to 50 000 cps measured using a Brookfield viscometer; preferably ranging from 10 to 50 000 cps; more ranging from 10 to 10 000 cps; even more preferably ranging from 10 to 4 000 cps; and most preferably ranging from 10 to 2 500 cps.
  • the oligomeric product has a number average molecular weight (Mn) ranging from 120 to 700 g/mol measured using gel permeation chromatography and a polystyrene calibration; preferably from 150 to 650 g/mol; and more preferably from 200 to 550 g/mol.
  • Mn number average molecular weight
  • the oligomeric product has a weight average molecular weight (Mw) ranging from 100 to 10,000 g/mol measured using gel permeation chromatography and a polystyrene calibration; preferably from 120 to 5,000 g/mol; more preferably from 150 to 3,500 g/mol; and even more preferably from 200 to 2,000 g/mol.
  • Mw weight average molecular weight
  • the oligomeric product has a z-average molecular weight (Mz) ranging from 100 to 100,000 g/mol measured using gel permeation chromatography and a polystyrene calibration; preferably from 120 to 85,000 g/mol; more preferably from 150 to 70,000 g/mol; and even more preferably from 200 to 50,000 g/mol.
  • Mz z-average molecular weight
  • the oligomeric product has a Mw/Mn ranging from 1.0 to 10.0; preferably from 1 .0 to 5.0; more preferably from 1 .0 to 4.0; and even more preferably from 1 .1 to 2.8.
  • the oligomeric product comprises a comonomer selected from the group consisting of styrene, alpha-methyl styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 4-t-butyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2,4-diisopropyl styrene, 2.4.6- trimethyl styrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl) styrene, 1 -vinyl naphthalene, 2-vinyl naphthalene, vinyl anthracene, 4-methoxy styrene, monochlorostyrene, dichlorostyrene, divinyl benzene, Indene, methyl-lndene, and mixtures thereof
  • the oligomeric product comprises a comonomer wherein the comonomer is present at a concentration ranging from 0.01 to 90 mol.% based on the total weight of the oligomeric product, preferably from 1.0 to 80 mol.%.
  • the oligomeric product is a wax; and/or it shows a crystal I izationn temperature (Tc) below 35°C; preferably ranging from 18 to 32°C; more preferably ranging from 20 to 30°C; and even more preferably ranging from 21 to 29°C.
  • Tc crystal I izationn temperature
  • the oligomeric product is a resin and/or it shows a glass transition temperature (Tg) below -20°C as determined by Differential Scanning calorimetry; preferably ranging from - 60°C to - 25°C; more preferably from -50°C to -30°C; and even more preferably from -49°C to - 35°C.
  • Tg glass transition temperature
  • a rubber composition comprising: a) At least one elastomer selected from synthetic and natural elastomers; b) A curing agent; and c) An oligomeric product prepared from a liquified waste polymer
  • the content of said at least one elastomer in the rubber composition ranges from 1 to 150 phr; preferably, from 1 to 120 phr; more preferably from 1 to 100 phr; from 50 to 150 phr.
  • the content of said curative agent in the rubber composition ranges from 0.1 - 25 phr; preferably, from 0.5 to 22 phr; more preferably from 1 to 20 phr, and even more preferably from 5 to 18 phr.
  • the content of said oligomeric product in the rubber composition ranges from 0.1 to 50 phr; preferably, from 0.5 to 40 phr; more preferably from 1 to 30 phr, and even more preferably from 5 to 25 phr.
  • the oligomeric product used in the rubber composition is having a number average molecular weight, Mn, ranging from 100 to 10 000 g/mol measured using gel permeation chromatography and a polystyrene calibration and wherein the oligomeric product shows a glass transition temperature (Tg) below -20°C as determined by Differential Scanning calorimetry or a crystallization temperature below 35°C.ln an embodiment, an adhesive composition comprising a tackifying resin comprising said oligomeric product is provided
  • the disclosure also provides for a process and an installation for the production of said oligomeric product.
  • the process for the preparation of an oligomeric product from a liquified waste comprises the following steps: a) providing a feedstream 1 containing liquified waste polymer, wherein said feedstream 1 contains at least 0.1 wt. % to at most 80 wt.
  • the process for the preparation of an oligomeric product comprises the following steps: a) providing a feedstream 1 containing liquified waste polymer, wherein said feedstream 1 contains at least 0.1 wt. % to at most 80 wt.
  • % of dienes based on the total weight of said feedstream 1 b) optionally, drying the feedstream 1 to obtain a dried feedstream 2; c) performing a polymerization reaction on said feedstream 1 or on the dried feedstream 2 under polymerization conditions to obtain a first product stream 3 comprising an oligomeric product; d) optionally, performing a neutralization reaction by contacting said first product stream 3 with a basic compound to obtain a neutralized product stream 4 and removing said basic compound from neutralized product stream 4 to obtain a second product stream 5; e) optionally, washing the first product stream 3 or the second product stream 5 with a solvent to obtain a washed stream 6; f) optionally, filtering the stream obtained in the previous step to obtain a filtered stream 7 wherein the filtering is performed to remove solids from the first product stream or from the second product stream 5 or from the washed stream 6, and/or to coalesce remaining traces of solvent if any; g) performing a separation to separate the oligomeric product from
  • the process for the preparation of an oligomeric product comprises the following steps: a) providing a feedstream 1 containing liquified waste polymer, wherein said feedstream 1 contains at least 0.1 wt. % to at most 80 wt.
  • % of dienes based on the total weight of said feedstream 1 b) drying the feedstream 1 to obtain a dried feedstream 2; c) performing a cationic polymerization reaction on the dried feedstream 2 under polymerization conditions to obtain a first product stream 3 comprising an oligomeric product; d) performing a neutralization reaction by contacting said first product stream 3 with a basic compound to obtain a neutralized product stream 4 and removing said basic compound from neutralized product stream 4 to obtain a second product stream 5; e) washing the second product stream 5 with a solvent to obtain a washed stream 6; f) filtering the washed stream 6 to obtain a filtered stream 7 wherein the filtering is performed to remove solids from the washed stream 6, and/or to coalesce remaining traces of solvent if any; g) performing a separation to separate the oligomeric product from the purified liquified waste polymer.
  • the disclosure also provides an installation 100 for carrying out a process for the preparation of an oligomeric product, said installation is remarkable in that it comprises: a polymerization section C comprising one or more polymerization reactors 23; an optional neutralization section D; a separation section comprising a separation unit 32 comprising one or more distillation columns. wherein the polymerization section C and the separation section are fluidically connected in series, and wherein the neutralization section D when present is placed downstream of the polymerization section and upstream of the separation section.
  • the disclosure also provides an installation 100 for carrying out a process for the preparation of an oligomeric product, said installation is remarkable in that it comprises, fluidically connected in the given order: an optional pre-treatment section A; an optional drying section B; a polymerization section C comprising one or more polymerization reactors 23; an optional neutralization section D; an optional washing section E; an optional filtering section; and a separation section comprising a separation unit 32 comprising one or more distillation columns.
  • the disclosure also provides an installation 100 for carrying out a process for the preparation of an oligomeric product, said installation is remarkable in that it comprises: a pre-treatment section A comprising a pyrolysis unit 11 , one or more separation units (13, 16, 19), and an optional washing unit 18; a drying section B comprising a decanter and/or a centrifuge 21 ; and/or a molecular sieve 22; a polymerization section C comprising one or more polymerization reactors 23; preferably loaded with an acidic catalyst; a neutralization section D a mixing reactor 24 and an optional separation unit 26 comprising at least one selected from a decanter, a centrifuge, and a filter; a washing section E comprising a mixing vessel 28 and a separation unit 30 comprising a decanter and/or a centrifuge; a filtering section comprising a filter and an optional molecular sieve 31 ; and a separation section comprising a separation unit 32 comprising one or more distillation columns.
  • the feedstream 1 used in the process contains a liquified waste polymer.
  • the liquified waste polymer is originated from the pyrolysis of plastic waste 10, so that the liquified waste polymer is a pyrolysis plastic oil.
  • step a) of providing a feedstream 1 comprises the preliminary steps of preparation of liquified waste polymer including: a1) providing a waste stream 10 being preferably a waste plastics stream; a2) pyrolyzing said waste stream 10 at a temperature of at least 200°C; a3) recovering a pyrolizer effluent 12 and separating said pyrolizer effluent into a C1 to C4 hydrocarbons fraction 14, a fraction 17 having a boiling range higher than 350°C and a remaining fraction being said pyrolysis plastic oil.
  • the installation 100 may comprise a pretreatment section A comprising a pyrolysis unit 11 , one or more separation units (13, 16, 19), and an optional washing unit 18.
  • the pretreatment section A comprises one or more separation units selected from: a first separation unit 13 to remove pyrolysis gas comprising a gas-liquid separator a second separation unit 16 to remove the fraction having a boiling range higher than 350°C comprising one or more distillation columns; and a third separation unit 19 to remove particles and gums, comprising a filter and/or a centrifuge
  • the process further comprises a further preliminary step of treatment of the fraction having a boiling range higher than 350°C and therefore further comprises a step a4) of sending said fraction having a boiling range higher than 350°C into a Fluid Catalytic Cracking (FCC) unit, or a hydrocracking unit, a coker or a visbreaker; or of blending said fraction having a boiling range higher than 350°C in crude oil or in a crude oil cut to
  • FCC Fluid Catalytic Cracking
  • liquified waste plastics comprise mainly pyrolysis plastic oil.
  • Pyrolysis plastic oil is produced from plastic wastes that are pyrolyzed.
  • An example of a pyrolysis process for waste plastics is disclosed in US 8,895,790 or in US 2014/228606 and in WO2016/009,333.
  • mixed plastics e.g., waste plastics 10
  • pyrolysis unit 11 the waste plastics are converted via pyrolysis to a pyrolysis product, wherein the pyrolysis product 12 comprises a gas phase (e.g., pyrolysis gases, such as C1 to C4 gases, hydrogen (H 2 ), carbon monoxide (CO), carbon dioxide (CO 2 ) mainly) and a liquid phase being pyrolysis plastic oil.
  • a gas phase e.g., pyrolysis gases, such as C1 to C4 gases, hydrogen (H 2 ), carbon monoxide (CO), carbon dioxide (CO 2 ) mainly
  • a liquid phase being pyrolysis plastic oil
  • the plastic waste 10 may include post-consumer waste plastics, such as mixed plastic waste.
  • Mixed plastics can comprise non-chlorinated plastics (e.g., polyolefins, polyethylene, polypropylene, polystyrene, copolymers, etc.), chlorinated plastics (e.g., polyvinylchloride (PVC), polyvinylidene chloride (PVDC), etc.), and the like, or mixtures thereof.
  • waste plastics 10 comprise long chain molecules or polymer hydrocarbons. Waste tires may also be used. Namely waste plastics may also include used tires.
  • the pyrolysis unit 11 may be any suitable vessel configured to convert waste plastics into gas phase and liquid phase products (e.g., simultaneously).
  • the vessel may be configured for gas phase, liquid phase, vapor-liquid phase, gas-solid phase, liquid-solid phase, or slurry phase operation.
  • the vessel may contain one or more beds of inert material or pyrolysis catalyst comprising sand, zeolite, alumina, a catalytic cracking catalyst, or combinations thereof.
  • the pyrolysis catalyst is capable of transferring heat to the components subjected to the pyrolysis process in the pyrolysis unit.
  • the pyrolysis unit 11 can be operated without any catalyst (e.g., pure thermal pyrolysis).
  • the pyrolysis unit 11 may be operated adiabatically, isothermally, nonadiabatically, non- isothermally, or combinations thereof.
  • the pyrolysis reactions of this disclosure may be carried out in a single stage or in multiple stages.
  • the pyrolysis unit 11 can be two reactor vessels fluidly connected in series.
  • the pyrolysis process may be divided into a first stage which is performed in a first vessel and in a second stage fluidly connected downstream of the first stage which is performed in the second vessel.
  • the second stage may enhance the pyrolysis of an intermediate pyrolysis product stream flowing from the first stage into the second stage, to yield a pyrolysis product flowing from the second stage.
  • the first stage may utilize thermal cracking of the waste plastics
  • the second stage may utilize thermal or catalytic cracking of the waste plastics to yield the pyrolysis product flowing from the second stage.
  • the first stage may utilize catalytic cracking of the waste plastics
  • the second stage may utilize thermal or catalytic cracking of the waste plastics to yield the pyrolysis product flowing from the second stage.
  • the pyrolysis unit 11 may include one or more equipments configured to convert mixed plastics into gas phase and liquid phase products.
  • the one or more equipments may or may not contain an inert material or pyrolysis catalyst as described above. Examples of such equipment include one or more of heated extruders, heated rotating kiln, heated tank-type reactors, packed bed reactors, bubbling fluidized bed reactors, circulating fluidized bed reactors, empty heated vessels, enclosed heated surfaces where plastic flows down along the wall and cracks, vessels surrounded by ovens or furnaces, or any other suitable equipment offering a heated surface to assist in cracking.
  • the pyrolysis unit 11 can be configured to pyrolyze (e.g., crack), and in some aspect (e.g., where hydrogen is added to the pyrolysis unit), additionally hydrogenate components of the waste plastics stream fed to the pyrolysis unit.
  • reactions which may occur in the pyrolysis unit 11 include, but are not limited to isomerization of one or more normal paraffins to one or more i- paraffins, selective ring opening of one or more cycloparaffins to one or more i-paraffins, cracking of long chain length molecules to short chain length molecules, removal of heteroatoms from heteroatom-containing hydrocarbons (e.g., dechlorination), hydrogenation of coke generated in the process, or combinations thereof.
  • a head space purge gas can be utilized in all or a portion of the pyrolysis stage(s) (conversion of waste plastics to a liquid phase and/or gas phase products) to enhance cracking of plastics, produce valuable products, provide a feed for steam cracking, or combinations thereof.
  • the head space purge gas may include hydrogen (H2), C1 to C4 hydrocarbon gases (e.g., alkanes, methane, ethane, propane, butane, isobutane), inert gases (e.g., nitrogen (N2), argon, helium, steam), and the like, or combinations thereof.
  • the use of a head space purge gas assists in the dechlorination in the pyrolysis unit, when the waste plastics comprises chlorinated plastics.
  • the head space purge gas may be introduced to the pyrolysis unit to aid in the removal of volatiles entrained in the melted mixed plastics present in the pyrolysis unit.
  • a hydrogen (H 2 ) containing stream can be added to the pyrolysis unit 11 to enrich the pyrolysis unit environment with H 2 , assist in stripping entrapped hydrogen chloride in the pyrolysis unit, provide a local environment rich in hydrogen in the pyrolysis melt or liquid, or combinations thereof; for example, via an H 2 containing stream fed directly to the pyrolysis unit 11 independently of the waste plastics 10 stream.
  • H 2 can also be introduced along with stream to the pyrolysis unit 11 , with adequate safety measures incorporated for hydrogen handling with plastics feed.
  • the pyrolysis unit 11 may facilitate any reaction of the components of the waste plastics 10 stream in the presence of, or with, hydrogen. Reactions may occur such as the addition of hydrogen atoms to double bonds of unsaturated molecules (e.g., olefins), resulting in saturated molecules (e.g., paraffins, i- paraffins, naphthenes). Additionally, or alternatively, reactions in the pyrolysis unit may cause a rupture of a bond of an organic compound, with a subsequent reaction and/or replacement of a heteroatom with hydrogen.
  • unsaturated molecules e.g., olefins
  • saturated molecules e.g., paraffins, i- paraffins, naphthenes
  • the use of hydrogen in the pyrolysis unit 11 can have beneficial effects of (I) reducing the coke as a result of cracking, (II) keeping the catalyst used (if any) in the process in an active condition, (III) improving removal of chloride from a stream such that the pyrolysis product from pyrolysis unit 11 is substantially dechlorinated with respect to waste plastics stream, which minimizes the chloride removal requirement in units downstream of the pyrolysis unit, (IV) hydrogenating of olefins, (V) reducing diolefins in pyrolysis product, (VI) helping operate the pyrolysis unit 11 at reduced temperatures for same levels of conversion of waste plastics 10 stream in the pyrolysis unit, or combinations of (I) -(VI).
  • the pyrolysis processes in the pyrolysis unit 11 may be low-severity or high-severity.
  • Low-severity pyrolysis processes may occur at a temperature of less than about 450 °C; for example, at a temperature ranging from 250 °C to 450 °C, preferably from 275 °C to 425 °C, more preferably 300 °C to 400 °C, and may produce pyrolysis oils rich in mono- and di-olefins as well as a significant amount of aromatics.
  • High-severity pyrolysis processes may occur at a temperature of equal to or greater than about 450 °C; for example, at a temperature ranging from 450 °C to 750 °C, preferably from 500 °C to 700 °C, more preferably from 550 °C to 650 °C, and may produce pyrolysis oils rich in aromatics, as well as more gas products (as compared with low severity pyrolysis).
  • a pyrolysis product 12 can be recovered as an effluent from the pyrolysis unit 11 and conveyed (e.g., flowed, for example via pumping, gravity, pressure differential, etc.) to a pyrolysis separating unit (i.e. a first separation unit 13).
  • the pyrolysis product 12 can be separated in the pyrolysis separating unit into a pyrolysis gas 14 stream and a pyrolysis plastic oil further used in step a) of the present disclosure.
  • the first separation unit 13 may comprise any suitable gas-liquid separator, such as a vapor-liquid separator, oil-gas separators, gas-liquid separators, degassers, scrubbers, traps, flash drams, compressor suction drams, gravity separators, centrifugal separators, filter vane separators, mist eliminator pads, liquid-gas coalescers, distillation columns, and the like, or combinations thereof.
  • a gas-liquid separator such as a vapor-liquid separator, oil-gas separators, gas-liquid separators, degassers, scrubbers, traps, flash drams, compressor suction drams, gravity separators, centrifugal separators, filter vane separators, mist eliminator pads, liquid-gas coalescers, distillation columns, and the like, or combinations thereof.
  • said of pyrolysis plastic oil originates directly from the pyrolysis of plastic wastes without further chemical transformation or separation.
  • the feedstream 1 contains only liquified waste polymer even more preferably only pyrolysis plastic oil.
  • the feedstream 1 contains at least 10 wt. % of liquified waste polymer based on the total weight of the feedstream 1 ; preferably at least 25 wt. %, more preferably at least 50 wt. %, even more preferably at least 75 wt. %.
  • the feedstream 1 may contain 100 wt.% of said liquified waste polymer based on the total weight of the feedstream 1 ; preferably at most 95 wt. %; more preferably, at most 90 wt. %; even more preferably at most 85 wt. %, and most preferably at most 80 wt. %.
  • the rest can be for instance a diluent or other hydrocarbons.
  • the feedstream 1 presents a bromine number of at most 150 g Br 2 / 100g as measured according to ASTM D1159-07(2017), preferably at most 100 g Br 2 / 100g; more preferably at most 80 g Br 2 / 100g, and even more preferably, at most 50 g Br 2 / 100g.
  • the liquified waste polymer in the feedstream 1 has a starting boiling point of at least 15°C and a final boiling point of at most 700°C.
  • the final boiling point is at most 600°C; more preferably 560°C, even more preferably 450°C even more preferably 350°C, the most preferred 250°C.
  • step a) of providing a feedstream 1 comprises one or more sub-steps of pre-treatment of the liquified waste polymer.
  • pre-treatment may be necessary before purifying the liquified waste polymer in the inventive process. Namely, before purifying the liquified waste polymer in the inventive process, the following pre-treatment may be considered either on the liquified waste polymer or on the feedstream 1 .
  • the liquified waste polymer or the feedstream 1 may be pretreated in a washing or a desalting unit 18 to remove water-soluble salts before being treated in the inventive process.
  • the liquified waste polymer or the feedstream 1 may be pretreated in a separation unit 19 to extract the particles and gums 20 by filtration, centrifugation, or a combination of the two technics before being treated in the inventive process.
  • the liquified waste polymer or the feedstream 1 is pretreated in a dewatering unit (i.e. , a drying unit) to remove water in said hydrocarbon stream to reach a water content of less than 0.1 vol.% preferably of less than 0.05 %vol according to ASTM D95-13(2018) before being treated in the inventive process, even more preferably said liquified waste polymer may be decanted.
  • a dewatering unit i.e. , a drying unit
  • the feedstream 1 is dried before being sent to the polymerization unit, step b) of drying can be performed a sub-step b1) of decantation and/or centrifugation; with preference, the substep b1) is followed by a sub-step b2) of drying using a molecular sieve 22 to reach a water content of less than 0.1 vol.% according to ASTM D95-13 (2016).
  • the installation 100 may comprise a drying section B comprising: a decanter and/or a centrifuge 21 ; and/or a molecular sieve 22 a polymerization reaction on the feedstream 1 or the dried feedstream 2 section C
  • Step c) comprise performing a polymerization reaction being a cationic polymerization or a free radical polymerization or an anionic polymerization; with preference, the polymerization reaction is a cationic polymerization.
  • the polymerization section C comprising one or more polymerization reactors 23 loaded with a catalyst; preferably an acidic catalyst.
  • said polymerization is an anionic polymerization.
  • said anionic polymerization is performed using an organolithium containing anionic initiator and terminated by reaction with a proton donating termination agent selected to form the lithium salt which can be filtered.
  • the installation comprises a polymerization section C comprising one or more polymerization reactors 23 loaded with an acidic catalyst.
  • said polymerization is a free radical polymerization.
  • said free radical polymerization is performed with an initiator utilized to generate an initial radical leading to monomer propagation followed by a termination via combination or disproportionation.
  • the polymerization reaction is a cationic polymerization.
  • step c) is performed in the presence of an acidic catalyst; with preference, the acidic catalyst is a Brdnsted acid ora Lewis acid; preferably a Lewis acid in the form of a transition metal halogenate.
  • Friedel - Crafts catalysts are strong Lewis acid catalysts that polymerize monomers via a cationic polymerization reaction mechanism.
  • examples of Friedel - Crafts catalysts that may be used to polymerize a monomer feed comprising pyrolysis oil include, but are not limited to, boron trifluoride, aluminum trichloride, tin tetrachloride, titanium trichloride, titanium tetrachloride, iron chloride ( III ), aluminum tri-bromide, dichloromono ethyl aluminum, and complexes thereof, such as boron trifluoride - phenol complex, boron trifluoride - ethanol complex, boron trifluoride - ether complex and the like, especially, boron trifluoride - phenol complex and boron trifluoride - ethanol complex.
  • the Friedel - Craft catalyst may also include a liquid aluminum chloride I hydrochloric acid I substituted aromatics complex, the aromatic being for example o-xylene, mesitylene, ethyl benzene, isopropyl benzene, and the like, such as short or long-chain alkylbenzenes.
  • the alky chain may be linear or branched and may vary from 2 to 30 carbon atoms.
  • Acidic liquid AICI obtained as by-products during the alkylation of benzene or any other substituted aromatics (toluene, xylenes) with branched-chain olefins may also be used.
  • the branched-chain olefins may be produced via the boron trifluoride oligomerization of propylene and fractionation (e. g. Ci 2 olefins or C 24 olefins may be alkylated with aromatics).
  • the Friedel - Crafts catalysts most preferred are AICI 3 and BF 3 .
  • step c) is performed in the presence of an acidic catalyst being a Lewis acid chosen among BF 3 , complexes of boron trifluoride, Al Cl 3 , SnCI 4 , ZnCI 2 , FeCI 3 and TiCI 3 , alkyl aluminum chlorides, H 2 SO 4 or any mixture thereof.
  • an acidic catalyst being a Lewis acid chosen among BF 3 , complexes of boron trifluoride, Al Cl 3 , SnCI 4 , ZnCI 2 , FeCI 3 and TiCI 3 , alkyl aluminum chlorides, H 2 SO 4 or any mixture thereof.
  • BF 3 refers to BF 3 in the gaseous form.
  • a particularly suitable complex of boron trifluoride is boron trifluoride etherate.
  • step c) is performed in the presence of an acidic catalyst being a Lewis acid with an acidic catalyst concentration ranging from 0.5 wt. % to 5.0 wt. % based on the total weight of said feedstream 1 ,
  • the reactions conditions include a contact time of at least 5 min to at most 5 hours.
  • step c) is performed under inert atmosphere, preferably under N 2 atmosphere.
  • the resins described herein may be prepared by a continuous solution polymerization process wherein the Friedel - Craft catalyst, optional comonomers, and a suitable aromatic or aliphatic hydrocarbon solvent, such as, for example, toluene, xylene, or heptane, are continuously added to a reactor vessel to form the desired homopolymer or copolymer.
  • the pyrolysis oilbased polymers may be prepared through a batch process in which all the initiator, monomers, and solvent are combined in the reactor together and mixed.
  • the acid catalyst may also be a solid catalyst.
  • the mass flow rate of the catalyst feed is from 0. 01 to 20 wt. % based on the total mass flow rate of monomer feed and catalyst feed; preferably, from 0.1 to 5 wt. %, and more preferably from 0.1 to 3 wt. %.
  • the reaction temperature of the mixture in the reactor vessel is also preferably maintained at a temperature of about - 10 to 50° C., when using BF, as the Friedel - Crafts catalyst and about 10 to 60°C, when using AICI 3 .
  • the low molecular weight pyrolysis oil-based homopolymers or copolymers resins according to the embodiments of the present invention are liquid resins with a number average molecular weight between 100 and 10,000 g/mol and more preferably 250 and 4,000 g/mol, as measured via gel permeation chromatography and converted using polystyrene calibration.
  • the cationic polymerization is performed in the presence of an acidic catalyst, being preferably chosen among BF 3 , AICI 3 , SnCI 4 , and TiCI 3 , ion exchange resin, CI 2 AIEt, H 2 SO 4 or any mixture thereof.
  • an acidic catalyst being preferably chosen among BF 3 , AICI 3 , SnCI 4 , and TiCI 3 , ion exchange resin, CI 2 AIEt, H 2 SO 4 or any mixture thereof.
  • At least one of AICI 3 , and BF 3 may be used to polymerize a monomer feed comprising pyrolysis oil and a comonomer in which the comonomer content of the monomer feed is ⁇ 90 wt. %, ⁇ 40 wt. %, ⁇ 25 wt. %, or ⁇ 15 wt. %, based on the total moles of the monomer in the monomer feed.
  • the polymerization initiator is BF 3 .
  • the acidic catalyst can be a solid acidic catalyst.
  • the preferred solid acid catalyst includes molecular sieves such as zeolite or silicalite.
  • the use of a solid acidic catalyst is particularly advantageous.
  • the solid acid catalyst can be easily separated. When a solid acid catalyst is used, the use of a neutralization step d) and step of washing e) may not be required.
  • step c) is performed with a solid acid catalyst being a molecular sieve, preferably selected among the topologies MFI, BEA, FAU, MEL, and the polymerization conditions comprise a Liquid Hourly Space Velocity (LHSV) ranging from 0.5 to 5.0 h’ 1 .
  • the molecular sieve contains one or more heteroatoms selected from Ti, Sn, Mo, W, Fe, Ni, Co, Cu, Zr, Hf, Nb, and Ta.
  • step c) is performed with a solid acid catalyst being an ion exchange resin, preferably a sulfonic ion-exchange resin such as Amberlyst A15 or A35 and the polymerization conditions comprise an LHSV ranging from 0.5 to 5.0 h -1 .
  • Ion exchange resin includes macro- porous polymeric resins having acidic properties for instance having the capability to exchange H + ions.
  • ion exchange resins can comprise styrene-divinylbenzene copolymers such as for instance Amberlyst resins.
  • the ion exchange resin is an Amberlyst 15.
  • step c) is performed with a solid acid catalyst being a clay or an activated clay and the polymerization conditions comprise an LHSV ranging from 0.5 to 5.0 h’ 1 .
  • step c) When an acidic catalyst soluble is used in step c) to produce the first product stream 3, it may be required to perform a neutralization step d1) preferably followed by a washing step d2).
  • the installation 100 comprise a neutralization section D comprising a mixing reactor 24 and an optional separation unit 26 comprising at least one selected from a decanter, a centrifuge, and a filter.
  • Step d) is a neutralization step that can be done by adding a base directly on said first product stream 3.
  • a basic compound, generally solid is put in contact with said first product stream 3, the mixture obtained is then agitated for at least 1 second to at most 24h, preferably during at least 1 minute to at most 12h. After agitation, the remaining base in the form of a solid is separated from the liquid, said liquid being said second product stream 5.
  • the neutralization step can also be done by washing said first product stream 3 with a basic compound 25 being a basic solution.
  • Basic aqueous solutions are preferred, basic aqueous solutions containing NaOH and/or NH 4 OH are the most preferred type of solution.
  • the basic solutions are put in contact and agitated for at least 1 second to at most 24h, preferably for at least 1 minute to at most 12h .
  • the mixture is let for separation to remove the second product stream 5 (being the organic phase) from the aqueous phase.
  • the separation can consist for instance in a decantation.
  • the decantation is known per se, it consists in letting the immiscible organic and aqueous phases being separated with the help of gravity.
  • the neutralization step can also be done by putting simultaneously or successively one or more basic compounds 25, preferably a base containing alkali/alkaline earth metals, more preferably a solid base such as LiOH, NaOH, CsOH, Ba(OH) 2 , Na 2 O, KOH, K 2 O, CaO, Ca(OH) 2 , MgO, Mg(OH) 2 or any mixture thereof or any strong base alone or in mixture, and a basic aqueous solution in contact with said first product stream 3.
  • a base containing alkali/alkaline earth metals more preferably a solid base such as LiOH, NaOH, CsOH, Ba(OH) 2 , Na 2 O, KOH, K 2 O, CaO, Ca(OH) 2 , MgO, Mg(OH) 2 or any mixture thereof or any strong base alone or in mixture
  • a basic aqueous solution in contact with said first product stream 3.
  • step d) is performed in continuous mode, namely the addition of fresh basic compound is performed on the first product stream 3 at the entry of for instance a mixing reactor 24 while simultaneously, at the exit of the mixing reactor 24 the spent basic compound is removed to obtain the second product stream 5.
  • the basic compound comprises an alkali metal cation, alkaline earth metal cation, and ammonium quaternary base, being preferably chosen among TMAOH, TEAOH, TBAOH, TPAOH, or any mixture thereof.
  • the washing step e) comprises washing the first product stream 3 or the second product stream 5 with a solvent 27 to obtain a washed stream 6.
  • the washing step e) is performed after the neutralization step d) to remove traces of the basic compound 25.
  • the washing step is performed with a ratio of said second product stream 5, or optionally of said neutralized product stream 4, over said solvent 27ranging from 0.05 to 20.
  • the washing is performed at a temperature ranging from 5°C to 95 °C, preferably under atmospheric pressure.
  • the washing can be performed in continuous mode or in batch mode.
  • the solvent is selected water or an acidic water solution, said solution comprising one or more organic acids like for instance citric acid (C 6 H 8 O 7 ), formic acid (CH 2 O 2 ), acetic acid (CH 3 COOH), sulfamic acid (H 3 NSO 3 ) or inorganic acids being hydrochloric acid (HCI), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 ) and any combination thereof.
  • organic acids like for instance citric acid (C 6 H 8 O 7 ), formic acid (CH 2 O 2 ), acetic acid (CH 3 COOH), sulfamic acid (H 3 NSO 3 ) or inorganic acids being hydrochloric acid (HCI), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 ) and any combination thereof.
  • the acidic solution has a pH ranging from 0.1 to 6.9.
  • the washing is preferably performed until the pH of said washed stream 6, or optionally on said second product stream 5, or neutralized product stream 4, is in the range of 5.0 to 9.0, preferably in the range of 6.0 to 8.0, even more preferably in the range of 6.5 to 7.5.
  • the washing is preferably followed by a decantation and/or a centrifugation to separate the solvent 27 from the washed mixture 29, to produce a washed stream 6.
  • the installation 100 may comprise a washing section E comprising a mixing vessel 28 and a separation unit 30 comprising a decanter and/or a centrifuge.
  • the optional filtering step f) and the filtering section can comprise a filtering step f) comprising filtering the stream obtained in the previous step to obtain a filtered stream 7 wherein the filtering is performed to remove solids.
  • the process may comprise a filtering step f) comprising filtering the washed stream 6 (i.e., the stream obtained in the previous step) to obtain a filtered stream 7 wherein the filtering is performed to remove solids from the washed stream 6, and/or to coalesce remaining traces of solvent if any.
  • a filtering step f comprising filtering the washed stream 6 (i.e., the stream obtained in the previous step) to obtain a filtered stream 7 wherein the filtering is performed to remove solids from the washed stream 6, and/or to coalesce remaining traces of solvent if any.
  • the filtering comprises a first sub-step of filtering to remove solids and/or to coalesce remaining traces of solvent if any, preferably followed by a second sub-step of dewatering preferably using a molecular sieve to reach a water content of less than 0.1 vol.% preferably of less than 0.05 %vol according to ASTM D95 -13 (2018) on the filtered stream 7.
  • the installation 100 may comprise a filtering section comprising a filter (not represented) and an optional molecular sieve 31.
  • the process comprises a step g) of performing a separation to separate the oligomeric product 33 from the purified liquified waste polymer 34.
  • step g) of separation is performed via distillation or steam distillation or vacuum stripping or fractional distillation or any combination.
  • the installation comprises a separation unit 32 comprising one or more distillation columns.
  • the oligomeric product 33 obtained can also be used further converted into valuable as valuable resins.
  • the oligomeric product 33 may be recovered and mixed with an elastomer, a curing agent, and a filler to obtain a rubber composition or is used as a tackifying resin and mixed with an elastomer to form an adhesive composition.
  • the process may comprise a step of separating and recovering a fraction having a boiling range higher than 350°C, preferably higher than 300°C.
  • This fraction can be recovered from any of the purified liquified waste polymer 34, the filtered stream 7, the washed stream 6, the second product stream 5, the neutralized product stream 4, the first product stream 3, the dried feedstream, or the feed stream 1 .
  • the fraction having an initial boiling point of at least 350°C, preferably at least 300°C can therefore be removed and sent into an FCC unit, or a hydrocracking unit, a coker or a visbreaker or blending said fraction having a boiling range higher than 350°C in crude oil or in a crude oil cut to be further refined.
  • the purified liquified waste polymer 34 is recovered and blended in the fuel pool; with preference, the purified liquified waste polymer is separated in a naphtha cut having a boiling range of less than 150°C and a diesel cut having a boiling range between 150 and 350°C wherein said naphtha cut is incorporated in a naphtha pool, said diesel cut is incorporated in a diesel pool.
  • the process further comprises a step h) of preparing a rubber composition comprising at least one elastomer selected from synthetic and natural elastomers; a curing agent; and said oligomeric recovered at step g).
  • the disclosure also provides a method to produce an adhesive composition
  • a method to produce an adhesive composition comprising the production of an oligomeric product according to the process of the fifth aspect, and mixing the recovered oligomeric product with an elastomer to form an adhesive composition; wherein the oligomeric product is a liquid resin prepared from a liquified waste polymer and used as a tackifying resin.
  • the determination of the diene content is performed with the help of the GPC with a UV detector.
  • a given quantity of maleic anhydride is added in the pyrolysis plastic oil and let to react with the dienes via the Diels-Alder reaction.
  • the reduction of the UV active MA peak in the chromatograph is monitored and used to determine diene concentration.
  • a calibration curve is prepared. The equipment used are
  • Agilent 1260 Series Degasser Part Number G1322A
  • Agilent 1260 Series Isocratic Pump Part Number G1310B
  • Agilent 1260 Series Autosampler Part Number G1329B
  • Agilent 1260 Series Thermostatted Column Compartment Part Number G1316A
  • Agilent 1260 Series Multiple Wavelength Detector Part Number G1365C
  • Agilent 1260 Series Refractive Index Detector Part Number G1362A.
  • Solvent THF Stabilized with 250 ppm BHT Flow Rate: 0.45 ml/min.
  • the chromatograph at 240 nm was analyzed for peak area.
  • the solution is let sit overnight and filtered the following day. This will remove some undissolved MA that has precipitated out.
  • the concentration of the MA solution is checked using the equation from the GPC-UV calibration in the following (Equation 1.): where PA is the peak area (15.8-16.6 min) at 240 nm (mV.s), sample M.F is the concentration of the sample ( samp fe TH F > and loj- Vol is the sample injection volume (uL). The equation 0.1586x + 0.3095 is the equation of the line from the MA calibration plot. iii) Preparation of sample and Diels-Alder (D-A) reaction. Weight out 15g of sample (pyrolysis oil) and add to a 100 mL round bottom flask (RBF).
  • D-A Diels-Alder
  • the sample in THF in the 20 mL vial will be used for the initial determination of MA for the diene calculation. Notated as initial in calculations. Run GPC-UV.
  • the initial amount of MA is calculated using equation 1 and the initial sample.
  • the final amount of MA is calculated using equation 1 and the final sample.
  • the Mw (g/mol) of the higher Mw dienes is determined using the Mw (g/mol) from the GPC and normalizing it using the Mw of the C5H8 peak and 68 g/mol.
  • Pyrolysis Oil 1 it has a boiling point ranging from 50°C to about 480°C and a Diene value of about 2.7 %.
  • the chlorine content is in the range of about 115 ppm
  • the silicium content is expected in the range of about 15 ppm.
  • the oxygen content is expected in the range of about 1 wt.%.
  • the nitrogen is expected in the range of about 1150 ppm wt.
  • Pyrolysis Oil 2 A light cut obtained by distillation of a pyrolysis oil (issued from a non-catalytic pyrolysis of mixed waste plastic) and having a boiling point ranging from about 50°C to about 260°C. The water is expected to be below 100ppm weight. The Diene value is expected to be in the range of about 4.8 %.
  • Pyrolysis Oil 3 A light cut of non-catalytic pyrolysis plastic oil (obtained by staged condensation of the pyrolysis effluent) and having a boiling point ranging from ⁇ 36°C to about 260°C. This oil has been decanted to assure a water content below 100ppm weight. The Diene value is expected to be in the range of about 7.8 %.
  • Pyrolysis Oil 4 it has a boiling point ranging from 40°C to about 401 °C and a Diene value of about 2.1 %.
  • the chlorine content is expected in the range of about 270 ppm
  • the silicium content is expected in the range of about 12 ppm.
  • the oxygen content is expected in the range of about 0.3 wt.%.
  • the nitrogen is expected in the range of about 1250 ppm wt.
  • the purification of pyrolysis oil was prepared through solution polymerization wherein the catalyst and monomers were continuously fed into the reaction vessel and boron trifluoride diethyl etherate is used as the catalyst with the BF 3 weight percentage on the total feed being 1.15 +/- 0.25%.
  • the flow rate of the monomer feed and the Friedel-Craft catalyst is controlled so that the catalyst feed is about 2 to 3 wt.% on the combined mass flow of the monomer.
  • the reaction temperature was maintained at 40°C throughout the polymerization process and all steps carried out under a nitrogen blanket.
  • reaction mixture was then transferred to a separatory funnel and washed three times with ⁇ 0.1 M NH4OH, discarding the aqueous phase.
  • the organic mixture was then washed twice more with water and the organic phase transferred to a separate three neck round bottom flask for distillation. During the washings, there is an insoluble tarry like residue that remains on the sides of the reaction flask and separatory funnel. In all cases of purification, the tarry residue was left behind unless otherwise noted.
  • the organic mixture was purged with nitrogen while being heated to 230°C and the volatile organics were collected. Once the temperature reached 230°C the distillation continued until there were no more volatiles being distilled at which point the nitrogen was replaced by steam.
  • the volatiles collected prior to steam stripping are referred to as the distillate.
  • Oligomeric product and steam condensate were collected until there was minimal oligomeric product being collected.
  • the oligomeric product collected is referred to as oily polymer.
  • the material remaining after steam stripping is a resin/wax product polymerized during purification.
  • the distillate collected is the purified pyrolysis oil with the dienes reduced.
  • Table 1 shows the catalyst and comonomer amounts used for polymerization and the final diene concentration of the distillate following purification.
  • the diene content has been reduced to less than 0.5% in all cases and in some instances, removed to undetectable levels, following polymerization.
  • Table 1. Initial and final diene concentration.
  • Example 2 Production of an oligomeric product using Aluminum Chloride (AlCh) as catalyst.
  • AlCh Aluminum Chloride
  • Hexanes (10 wt.% of the total) was added to a RBF purged with nitrogen.
  • the AlCh catalyst approximately 1 .25 wt.% of the total feed, was then added to the hexanes and warmed to 35°C while stirring under nitrogen.
  • the pyrolysis oil feed was measured out in an individual flask and fed at a rate of 2 mL/min. Upon completion of the feed addition, the mixture was stirred at 35°C for 50 minutes before cooling to room temperature. The polymerization was carried out under a nitrogen blanket.
  • reaction mixture was then transferred to a separatory funnel and washed three times 25% aqueous isopropanol (IPA), discarding the aqueous phase.
  • IPA aqueous isopropanol
  • the organic mixture was then washed twice more with water and the organic phase was transferred to a separate three neck round bottom flask for distillation. The organic mixture was then distilled, and steam stripped as in example 1 .
  • Example 3 Production of an oligomeric product using Amberlyst 15 as catalyst.
  • Example 4 Production of an oligomeric product using sulfuric acid (H2SO4). Pyrolysis oil was added to a RBF and stirred at room temperature. Sulfuric acid, approximately 2.5 wt.% on total feed, was then added to the stirring pyrolysis oil and there was an immediate exotherm. The reaction was stirred until the temperature dropped back to room temperature. The acid was neutralized, and the oil washed with dilute sodium carbonate (2x) followed by water (2.x). The oil was then distilled, and steam stripped as in example 1.
  • H2SO4 sulfuric acid
  • the resin or wax products derived from pyrolysis oil are a result of the cationic polymerization used on the pyrolysis oil.
  • the resin or wax is generated and isolated, then the resulting liquid hydrocarbon is a purified pyrolysis oil.
  • the oligomeric products are of various kind in those examples. Namely the wax+ product is constituted of the tarry residue that remains after the aqueous washes was dissolved in acetone/THF and added to the organic phase for distillation.
  • the isolated residue that remains following distillation and steam stripping of the post-polymerized pyrolysis oils are the resin or wax products dependent on the pyrolysis oil feed.
  • the reaction conditions and product properties are shown in Table 3.
  • the properties of the oligomeric products are dependent on the plastic pyrolysis oil feed and in all cases the diene content has been reduced.
  • the aromatic content in the wax+ and wax products from pyrolysis oil 1 are relatively low and these are highly saturated hydrocarbon products.
  • the melting and crystallization temperature of the wax+ and wax products being around room temperature.
  • the resin and resin-sty products from the polymerization of pyrolysis oil 2 contain higher amount of aromatic content.
  • the resin and wax products from the polymerization of pyrolysis oils 2 and 1 respectively were evaluated against Wingtack 10 (WT10, our reference) as processing aids in a basic tape formulation made up of the following components: Adhesive compositions were mixed in an open-top sigma blade mixer at 177°C (350°F) under a nitrogen blanket. All mixing times were kept to less than 60 minutes to minimize degradation of the styrenic block copolymer (SBC). First, the SBC and BNX 1010 antioxidant (AO) were combined and masticated for 5-10 minutes until smooth. The resin was added incrementally over several minutes to ensure good mixing and to prevent separation; once all the resin was added the formulation was mixed for 20-30 minutes. Finally, the processing aid was added slowly while mixing and then mixed for another 10 minutes. The adhesive was transferred to a suitable container coated with a release liner to facilitate easy removal once cool.
  • WT10 Wingtack 10
  • the viscosities of the adhesive formulations were measured at 160°C and can be seen in Figure 4.
  • the viscosity of the formulations with the resin and wax are 24 and 48 percent less than the formulation using Wingtack , respectively.
  • the decrease in molten viscosity should allow for the reduction of the temperature needed for coating which translates to energy savings.
  • Wingtack 10 is a petroleum derived resin and was chosen as the control and is known to provide superior adhesive performance compared to process oil in low-T g block polymer PSAs, without creating the migration or shelf-life problems that process oils frequently cause. Therefore, performance of the pyrolysis-oil based resin superior to or equal to that of the control is indicative of improved performance relative to common processing oils.
  • the adhesives were coated onto 2 mil (50 micron) PET at an approximate thickness of 0.9 mils (22 microns) dry.
  • the adhesive coated PET was laminated to release paper and allowed to condition at 50% relative humidity and 23°C (73°F) a minimum of 24 hours before initial testing.
  • the adhesive coated PET laminated to release paper was placed in the oven at 70°C for 7 days before testing.
  • One inch and one-half inch strips were cut and tested according to methods detailed by the Pressure Sensitive Tape Council (PSTC).
  • PSTC Pressure Sensitive Tape Council
  • 180° peel adhesion testing was conducted using one-inch wide (2.54 cm) test specimen and stainless steel (SS), corrugated cardboard (CC), and high-density polyethylene (HDPE) test substrates. All adhesion test results are reported in pounds per square inch (psi). Loop tack and quick stick testing were conducted using the same three test substrates and reported in psi. Room temperature shear testing was conducted using specimens that were 0.5” wide with an overlap of 0.5” (total 1/4 in 2 contact area) and were tested using 0.5 kg weights and SS panels as well as unbleached kraft paper held to the test panels with double-sided tape. Heat resistance was determined by measuring the shear adhesion failure temperature (SAFT) and reported in °C. Test specimens for SAFT determination were one inch wide and had a contact area of 1 in 2 with a weight of 1 kg. All testing was conducted in triplicate and the averages reported.
  • SAFT shear adhesion failure temperature
  • Figure 5, Figure 6, and Figure 7 show the results of the 180° peel adhesion testing on SS, CC, and HDPE for the initial and aged samples.
  • the adhesion values for the resin-based adhesive is comparable to the control-based adhesive within the experimental error involved in the testing.
  • the adhesion values for the wax-based adhesive is comparable, within experimental error, to the control on CC.
  • Figure 11 , Figure 12, and Figure 13 show the quick stick results and similar performance of the resin and wax-based adhesives to the WT10 based adhesive on SS, HDPE, and CC.
  • the adhesives formulated with the resin and WT 10 exhibit stick slip on SS and HDPE during the quick stick test while the adhesive formulated with the wax does not have any stick slip on any of the tested substrates.
  • the results from the loop tack and quick stick tests indicate that the adhesives formulated using the resin and wax from the pyrolysis oil polymerizations have similar tack to the adhesive formulated using WT10.
  • the heat resistance of the adhesives formulated using the resin, wax, and WT10 as measured by SAFT are shown in Figure 16 and Figure 17.
  • the heat resistance of all three adhesive formulations is the same with experimental error on SS, and the resin material is similar on Kraft paper.
  • a model tire tread formulation was used to evaluate the resin and wax products described in Table compared to standard processing oils and Wingtack .
  • the formulations were compounded in three stages. The initial stage was compounded in an internal mixer at 150-155°C for 5 minutes, the second stage completed using an internal mixer at 90-100°C for 4 minutes, and the third stage at 60°C for 5 minutes. The mixing for all samples at each stage was similar and as the stages progressed the compounds became less fragmented.
  • Oscillating disk rheometer (ODR) tests were performed to compare the crosslinking behavior of the various batches at 160°C. The results are shown in the below Table.
  • the working time (ts2) for all of the tire tread formulations remains constant regardless of the processing oil used; however, the use of the resin and resin-sty from the pyrolysis oil increase the cure time (t’90) compared to the standard processing oils and WT10. Delta torque for the resin and resin-sty based formulations are less than that of WT10 while the wax+ and wax are similar.
  • the cured properties of the formulations are shown in the below table.
  • the formulations were cured at 160°C for 25 minutes in a heated press.
  • the resin and resin-sty products are comparable to WT10 as a processing oil in tire tread formulations.
  • the wax and wax+ products are comparable to TDAE when used as a processing oil in these formulations.
  • Dynamic mechanical analysis was used to determine the elastic modulus G’ as a function of strain deformation (the Payne effect) and measure tan 6.
  • the elastic modulus as a function of strain deformation is used to evaluate the effectiveness of the silica dispersion; at low deformation, decreased interaction between silica particles results in a lower G’ value indicative of better dispersion.
  • tan 5 is used as a performance indicator; a higher value of tan 5 at 0°C is associated with better wet traction and a lower value of tan 5 at 60°C is associated with better rolling resistance. The results are reported in the below table.
  • the wax products from pyrolysis oil polymerization improve the dispersion of silica in the formulations relative to the controls and the resin products perform like the standard oils.
  • the resin and resin-sty perform like WT10 and have improved wet traction compared to the standard processing oils in tire tread formulations while the wax products show improved rolling resistance compared to the standard processing oils.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

La présente invention concerne un produit oligomère préparé à partir d'huile de pyrolyse, de préférence une huile de pyrolyse de plastique, par polymérisation, de préférence une polymérisation cationique.
PCT/EP2023/069561 2022-07-14 2023-07-13 Produit oligomère obtenu a partir d'huile de pyrolyse par polymérisation WO2024013341A1 (fr)

Applications Claiming Priority (16)

Application Number Priority Date Filing Date Title
EP22315147.3 2022-07-14
EP22315152.3 2022-07-14
EP22315149 2022-07-14
EP22315148.1 2022-07-14
EP22315150.7 2022-07-14
EP22315150 2022-07-14
EP22315152 2022-07-14
EP22315148 2022-07-14
EP22315147 2022-07-14
EP22315146 2022-07-14
EP22315151.5 2022-07-14
EP22315153.1 2022-07-14
EP22315151 2022-07-14
EP22315153 2022-07-14
EP22315149.9 2022-07-14
EP22315146.5 2022-07-14

Publications (1)

Publication Number Publication Date
WO2024013341A1 true WO2024013341A1 (fr) 2024-01-18

Family

ID=87312079

Family Applications (8)

Application Number Title Priority Date Filing Date
PCT/EP2023/069558 WO2024013340A1 (fr) 2022-07-14 2023-07-13 Production d'éthylène et de propylène à partir d'huile de pyrolyse plastique
PCT/EP2023/069549 WO2024013333A1 (fr) 2022-07-14 2023-07-13 Procédé de recyclage d'huile issue de déchets plastiques
PCT/EP2023/069564 WO2024013343A1 (fr) 2022-07-14 2023-07-13 Produit de caoutchouc obtenu à partir d'huile de pyrolyse via une polymérisation
PCT/EP2023/069551 WO2024013335A1 (fr) 2022-07-14 2023-07-13 Procédé de purification d'huile issue de déchets plastiques à l'aide de composés basiques
PCT/EP2023/069561 WO2024013341A1 (fr) 2022-07-14 2023-07-13 Produit oligomère obtenu a partir d'huile de pyrolyse par polymérisation
PCT/EP2023/069555 WO2024013337A1 (fr) 2022-07-14 2023-07-13 Procédé de recyclage et de craquage d'huile issue de déchets plastiques
PCT/EP2023/069567 WO2024013345A1 (fr) 2022-07-14 2023-07-13 Produit adhésif fabriqué à partir d'huile de pyrolyse par polymérisation
PCT/EP2023/069546 WO2024013331A1 (fr) 2022-07-14 2023-07-13 Purification d'huile à base de déchets plastiques via une polymérisation

Family Applications Before (4)

Application Number Title Priority Date Filing Date
PCT/EP2023/069558 WO2024013340A1 (fr) 2022-07-14 2023-07-13 Production d'éthylène et de propylène à partir d'huile de pyrolyse plastique
PCT/EP2023/069549 WO2024013333A1 (fr) 2022-07-14 2023-07-13 Procédé de recyclage d'huile issue de déchets plastiques
PCT/EP2023/069564 WO2024013343A1 (fr) 2022-07-14 2023-07-13 Produit de caoutchouc obtenu à partir d'huile de pyrolyse via une polymérisation
PCT/EP2023/069551 WO2024013335A1 (fr) 2022-07-14 2023-07-13 Procédé de purification d'huile issue de déchets plastiques à l'aide de composés basiques

Family Applications After (3)

Application Number Title Priority Date Filing Date
PCT/EP2023/069555 WO2024013337A1 (fr) 2022-07-14 2023-07-13 Procédé de recyclage et de craquage d'huile issue de déchets plastiques
PCT/EP2023/069567 WO2024013345A1 (fr) 2022-07-14 2023-07-13 Produit adhésif fabriqué à partir d'huile de pyrolyse par polymérisation
PCT/EP2023/069546 WO2024013331A1 (fr) 2022-07-14 2023-07-13 Purification d'huile à base de déchets plastiques via une polymérisation

Country Status (1)

Country Link
WO (8) WO2024013340A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120149953A1 (en) 2010-12-13 2012-06-14 Chevron U.S.A. Inc. Process for making a high viscosity base oil with an improved viscosity index
US20140228606A1 (en) 2013-02-12 2014-08-14 Saudi Basic Industries Corporation Conversion of plastics to olefin and aromatic products with product recycle
US8895790B2 (en) 2013-02-12 2014-11-25 Saudi Basic Industries Corporation Conversion of plastics to olefin and aromatic products
WO2016009333A1 (fr) 2014-07-17 2016-01-21 Sabic Global Technologies B.V. Valorisation de courants à teneur insuffisante en hydrogène en utilisant des flux donneurs d'hydrogène dans un procédé d'hydropyrolyse
US20210189250A1 (en) * 2019-12-23 2021-06-24 Chevron U.S.A. Inc. Circular economy for plastic waste to polyethylene and chemicals via refinery crude unit
FR3116279A1 (fr) * 2020-11-16 2022-05-20 Compagnie Generale Des Etablissements Michelin Procédé de production de résines à partir de copeaux de caoutchouc

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2940830A (en) 1955-08-23 1960-06-14 Columbia Southern Chem Corp Method of preparing silica pigments
US3288872A (en) 1963-05-14 1966-11-29 Exxon Research Engineering Co Alkali metal polymerization of conjugated dienes
US3809680A (en) 1972-03-20 1974-05-07 Firestone Tire & Rubber Co Resinous formaldehyde reaction product of vulcanized-scrap-rubber pyrolysis oil and its production
JPS5639356B2 (fr) 1973-04-07 1981-09-12
US3911041A (en) 1974-09-23 1975-10-07 Mobil Oil Corp Conversion of methanol and dimethyl ether
FR2536752A1 (fr) * 1982-11-25 1984-06-01 Brossas Jean Resines liquides, reticulees, a base de polyolefines, et le procede de leur preparation
US4639259A (en) 1985-10-09 1987-01-27 Kaiser Aluminum & Chemical Corporation Promoted scavenger for purifying HCl-contaminated gases
US4762537A (en) 1985-11-07 1988-08-09 Aluminum Company Of America Adsorbent for HCl comprising alumina and acid-treated Y zeolite
JPH0689061B2 (ja) * 1988-12-16 1994-11-09 日本石油株式会社 ブタジエン低重合体付加物の製造方法
DK0502618T3 (da) 1991-03-05 1996-12-23 Bp Chem Int Ltd Polymerkrakning
DE4207976C2 (de) 1992-03-13 2001-03-15 Rwe Umwelt Ag Verfahren zur Herstellung Olefinen durch thermische Behandlung von Kunststoffabfällen
EP0568913A3 (fr) 1992-05-03 1995-03-22 Dalian Chemical Physics Inst Procédé pour la conversion de méthanol en oléfines légères et catalyseurs utilisés pour celle-ci.
US5316998A (en) 1992-05-05 1994-05-31 Discovery Chemicals, Inc. HCl adsorbent and method for making and using same
EP0710270B1 (fr) 1993-07-20 1997-01-02 Basf Aktiengesellschaft Procede de recyclage de matieres plastiques dans un vapocraqueur
US6797851B2 (en) 2001-08-30 2004-09-28 Exxonmobil Chemical Patents Inc. Two catalyst process for making olefin
EP2082802A1 (fr) 2008-01-25 2009-07-29 Total Petrochemicals Research Feluy Procédé pour l'obtention d'un composite catalyseur
EP2082801A1 (fr) 2008-01-25 2009-07-29 Total Petrochemicals Research Feluy Processus pour obtenir des tamis moléculaires modifiés
ES2646283T3 (es) 2008-02-07 2017-12-13 Total Research & Technology Feluy Deshidratación de alcoholes sobre silicatos cristalinos
JP5214752B2 (ja) 2011-02-21 2013-06-19 株式会社コナミデジタルエンタテインメント ゲームシステム、それに用いる制御方法及び、コンピュータプログラム
CN105814143A (zh) 2013-12-09 2016-07-27 盛禧奥欧洲有限责任公司 硅烷改性的弹性聚合物
DE102017221236A1 (de) 2017-11-28 2019-05-29 Continental Reifen Deutschland Gmbh Schwefelvernetzbare Kautschukmischung, Vulkanisat der Kautschukmischung und Fahrzeugreifen
US11512234B2 (en) * 2020-01-10 2022-11-29 Fina Technology, Inc. Farnesene-based tackifying resins and adhesive compositions containing the same
US20230416612A1 (en) * 2020-04-07 2023-12-28 Totalenergies Onetech Belgium Waste plastic based oil upgrading into high value chemicals via direct catalytic cracking

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120149953A1 (en) 2010-12-13 2012-06-14 Chevron U.S.A. Inc. Process for making a high viscosity base oil with an improved viscosity index
US20140228606A1 (en) 2013-02-12 2014-08-14 Saudi Basic Industries Corporation Conversion of plastics to olefin and aromatic products with product recycle
US8895790B2 (en) 2013-02-12 2014-11-25 Saudi Basic Industries Corporation Conversion of plastics to olefin and aromatic products
WO2016009333A1 (fr) 2014-07-17 2016-01-21 Sabic Global Technologies B.V. Valorisation de courants à teneur insuffisante en hydrogène en utilisant des flux donneurs d'hydrogène dans un procédé d'hydropyrolyse
US20210189250A1 (en) * 2019-12-23 2021-06-24 Chevron U.S.A. Inc. Circular economy for plastic waste to polyethylene and chemicals via refinery crude unit
FR3116279A1 (fr) * 2020-11-16 2022-05-20 Compagnie Generale Des Etablissements Michelin Procédé de production de résines à partir de copeaux de caoutchouc

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
F. SADAKA ET AL., POLYMER DEGRADATION AND STABILITY, vol. 98, 2013, pages 736 - 742
IUPAC: "Compendium of Chemical Terminology", 1997
ROZENTSVET V A ET AL: "Cationic Oligomerization of the Pyrolysis C5Fraction", PETROLEUM CHEMISTRY, PLEIADES PUBLISHING, MOSCOW, vol. 58, no. 8, 17 July 2018 (2018-07-17), pages 694 - 701, XP036550696, ISSN: 0965-5441, [retrieved on 20180717], DOI: 10.1134/S0965544118080200 *
ROZENTSVET V.A. ET AL.: "Petroleum Chemistry", vol. 58, 2018, PLEIADES PUBLISHING, LTD., pages: 694 - 701
SADAKA FATEN ET AL: "Telechelic oligomers obtained by metathetic degradation of both polyisoprene and styrene-butadiene rubbers. Applications for recycling waste tyre rubber", POLYMER DEGRADATION AND STABILITY, BARKING, GB, vol. 98, no. 3, 28 December 2012 (2012-12-28), pages 736 - 742, XP028577456, ISSN: 0141-3910, DOI: 10.1016/J.POLYMDEGRADSTAB.2012.12.018 *

Also Published As

Publication number Publication date
WO2024013337A1 (fr) 2024-01-18
WO2024013335A1 (fr) 2024-01-18
WO2024013333A1 (fr) 2024-01-18
WO2024013343A1 (fr) 2024-01-18
WO2024013345A1 (fr) 2024-01-18
WO2024013331A1 (fr) 2024-01-18
WO2024013340A1 (fr) 2024-01-18

Similar Documents

Publication Publication Date Title
EP0963365B1 (fr) Acides solides utilises comme catalyseurs pour la preparation de resines d'hydrocarbure
US6103808A (en) High aromatic oil and rubber composition and oil extended synthetic rubber using the same
EP0132315B1 (fr) Procédé de préparation de polymères de butylène avec des poids moléculaires de 400 à 5000
KR20140009165A (ko) 재생가능한 공급원으로부터의 이소부텐의 중합체
WO2005103092A1 (fr) PROCÉDÉ DE PRODUCTION D’UN POLYMÈRE α-OLÉFINIQUE
JPS5914044B2 (ja) 石油樹脂
JPS632966B2 (fr)
JPH0717808B2 (ja) 石油樹脂の製造方法
WO2024013341A1 (fr) Produit oligomère obtenu a partir d'huile de pyrolyse par polymérisation
KR20190095440A (ko) 폴리인단 수지를 포함하는 타이어 및 이의 용도
JPH0462772B2 (fr)
EP0057510B1 (fr) Production de résines hydrocarbonées et produits ainsi obtenus
US4403080A (en) Isomerization and polymerization of hydrocarbon resins
JP4863186B2 (ja) オレフィン重合体の製造方法
CN114752412B (zh) 在工艺水中抑制聚合的方法
CN107879875B (zh) 一种丙烷生产乙烯和丙烯的方法和装置
US2709695A (en) High-temperature polymerization of unsaturated hydrocarbon mixtures
CN107879887B (zh) 一种乙烷生产乙烯和丙烯的方法和装置
US3197519A (en) Removal of alkali metal from liquid hydrocarbon polymers
JPH0552352B2 (fr)

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23741708

Country of ref document: EP

Kind code of ref document: A1